CN111115589B - Method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential - Google Patents

Method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential Download PDF

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CN111115589B
CN111115589B CN202010013602.6A CN202010013602A CN111115589B CN 111115589 B CN111115589 B CN 111115589B CN 202010013602 A CN202010013602 A CN 202010013602A CN 111115589 B CN111115589 B CN 111115589B
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selenium
copper
tellurium
copper smelting
selenium powder
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CN111115589A (en
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杨斌
查国正
蒋文龙
徐宝强
刘大春
孔祥峰
罗欢
黄大鑫
郭新宇
邓聚海
陈秀敏
李一夫
郁青春
杨红卫
田阳
邓勇
王飞
熊恒
杨佳
吴鉴
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00Selenium; Tellurium; Compounds thereof
    • C01B19/02Elemental selenium or tellurium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00Obtaining copper
    • C22B15/0063Hydrometallurgy
    • C22B15/0065Leaching or slurrying
    • C22B15/0067Leaching or slurrying with acids or salts thereof
    • C22B15/0071Leaching or slurrying with acids or salts thereof containing sulfur
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention belongs to the technical field of metallurgical impurity removal, and particularly relates to a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential. The invention provides a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential, which comprises the following steps: mixing the copper smelting crude selenium powder to obtain selenium slurry; after the selenium slurry is subjected to first pH value adjustment, adding an oxidant to an oxidation potential, sequentially performing a first precipitation reaction and a first filtration to remove copper and lead in copper smelting crude selenium powder to obtain primary selenium; the oxidation potential is 400-800 mV; mixing the primary selenium and a reducing agent to a reduction potential, carrying out second pH value adjustment, and then sequentially carrying out second precipitation reaction and second filtration to remove tellurium in copper smelting crude selenium powder; the reduction potential is-400-0 mV. The test result shows that the method provided by the invention realizes the high-efficiency removal of impurities of copper, lead and tellurium in the copper smelting crude selenium powder.

Description

Method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential
Technical Field
The invention belongs to the technical field of metallurgical impurity removal, and particularly relates to a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential.
Background
Selenium is an important rare metal, and most of selenium is produced from copper smelting by-products. In the copper smelting process, the anode mud with high added value is produced by carrying out electrolytic refining on the crude copper, and the crude selenium powder for copper smelting can be produced by comprehensively recovering the copper anode mud through a pyrogenic process or a hydrometallurgy process. The typical copper smelting crude selenium powder comprises, by mass, 60-80% of Se, 1-10% of Te, 0.01-5% of Cu, 0.01-5% of Pb and H25-30% of O, and the balance of trace elements such As Fe, S, Sn, As, Ni and the like. The crude selenium powder for copper smelting needs to be purified to prepare high-purity selenium with the purity of 99.99 percent, so that the use requirements of advanced materials such as gallium selenide, bismuth oxide selenide, copper indium gallium selenide and the like can be met. Literature "technological research for purifying selenium and enriching gold and silver by vacuum distillation" (Mei Qing Song, search of the nation)Process research on purifying selenium and enriching gold and silver by vacuum distillation in Liu Dalichun, et al]University of Kunming science (Nature science edition), 2018, v.43: no.213 (02): 18-25), selenium slag is dried, smelted and distilled to produce selenium with the purity of 98%, and impurities difficult to remove are copper, lead and tellurium, so that the effective removal of the impurities of copper, lead and tellurium is a key problem and a main problem for realizing the high-purity preparation of crude selenium.
The impurities copper, lead and tellurium in the coarse selenium powder are mainly represented in the forms of simple substance of tellurium and selenium telluride of CuSe, PbSe, CuTe and PbTe, and Qiu's Bao et al (Qiu Bao, Wang Bao Cheng braiding, New development of rare noble metal metallurgy, publication of metallurgy industry, 2019 and 4 months) are mainly oxidized to oxidize selenium into volatile SeO2The smoke and the impurities are not easy to be oxidized, so that the separation of selenium and impurity elements is realized; SeO2Absorbing the smoke with aqueous solution to form selenite, and introducing SO2Reducing the selenium to precipitate refined selenium, in such a way that the main metal selenium is converted into SeO, although impurities are effectively removed2The toxic and harmful substances and the recovery rate of selenium in the oxidation and volatilization stage are low. The application of the oxidation slagging method in selenium and tellurium separation [ J ] in the experimental study of the selenium and tellurium separation process]Yunnan metallurgy, 2019 (4): 36-39) adopts a high-temperature oxidation slagging mode, can realize the removal of copper, lead and tellurium, and prepare 3N refined selenium, but the mode needs to be realized in a high-temperature selenium melt, which easily causes the oxidation of selenium and has poor operating environment. Patent CN1283549C discloses a process for extracting selenium by vacuum smelting, wherein crude selenium powder containing 20-90% of selenium by mass is granulated, dried, vacuum distilled to remove impurities and purify selenium, and 2-4% of tellurium as an impurity is not effectively removed in a final selenium product. Patent CN1298619C discloses a method for removing tellurium from crude selenium, which also adopts sodium hydroxide solution to treat crude selenium powder with alkali, dissolve impurity tellurium in the solution, and remove the impurity tellurium through filtration, but this method also dissolves selenium while dissolving Te, and needs to add acidification process to precipitate selenium from the solution again, the steps are long, and the recovery rate of selenium is low. In the above method, the impurity tellurium in the crude selenium powder is the same as the impurity tellurium in the crude selenium powder as the main metal element seleniumThe physical and chemical properties are very similar, the effective removal is difficult by adopting a distillation mode, and the purity of the selenium is difficult to further improve.
Disclosure of Invention
In view of the above, the invention aims to provide a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential, which realizes efficient removal of impurities copper, lead and tellurium in copper smelting crude selenium powder, and has the characteristics of high selenium yield, small selenium loss and simple process.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential, which comprises the following steps:
mixing the copper smelting crude selenium powder to obtain selenium slurry;
after the selenium slurry is subjected to first pH value adjustment, adding an oxidant to an oxidation potential, sequentially performing a first precipitation reaction and a first filtration to remove copper and lead in copper smelting crude selenium powder to obtain primary selenium; the oxidation potential is 400-800 mV;
mixing the primary selenium and a reducing agent to a reduction potential, carrying out second pH value adjustment, and then sequentially carrying out second precipitation reaction and second filtration to remove tellurium in copper smelting crude selenium powder; the reduction potential is-400-0 mV.
Preferably, the copper smelting crude selenium powder comprises the following chemical components in percentage by mass: se 60-80%, Te 1-10%, Cu 0.01-5%, Pb 0.01-5%, H25-30% of O, and the balance of trace impurity elements Fe, S, Sn, As and Ni.
Preferably, the particle size of the copper smelting crude selenium powder is 0.1-300 μm.
Preferably, after the first pH value is adjusted, the pH value of the obtained slurry is 1-4.
Preferably, the oxidant is one or more of potassium permanganate, sodium hypochlorite, hydrogen peroxide and manganese dioxide.
Preferably, the first precipitation reaction is carried out under stirring conditions; the stirring speed is 30-300 rpm, and the time is 0.5-3 h.
Preferably, the reducing agent is a ferrous salt or a sulfite.
Preferably, after the second pH value adjustment, the pH value of the obtained slurry is 7-12.
Preferably, the second precipitation reaction is carried out under stirring conditions; the stirring speed is 30-1000 rpm, and the time is 0.5-3 h.
The invention provides a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential, which comprises the following steps: mixing the copper smelting crude selenium powder to obtain selenium slurry; after the selenium slurry is subjected to first pH value adjustment, adding an oxidant to an oxidation potential, sequentially performing a first precipitation reaction and a first filtration to remove copper and lead in copper smelting crude selenium powder to obtain primary selenium; the oxidation potential is 400-800 mV; mixing the primary selenium and a reducing agent to a reduction potential, carrying out second pH value adjustment, and then sequentially carrying out second precipitation reaction and second filtration to remove tellurium in copper smelting crude selenium powder; the reduction potential is-400-0 mV. Under the condition of a specific oxidation potential, impurities of copper and lead are converted into soluble ions so as to ensure that the impurities of copper and lead are removed after the first filtration; and regulating the system to a specific reduction potential to convert the impurity tellurium into soluble ions so as to ensure that the impurity tellurium is removed after the second filtration. According to the invention, a mode of controlling potential oxidation reduction twice is adopted, impurity elements of copper, tellurium and lead are selectively leached in different environments, meanwhile, the insolubility of a main element Se is ensured to enter a solution, and the impurity elements of copper, lead and tellurium in the crude selenium powder are efficiently removed step by step under the condition of simple process operation.
The test results of the embodiment show that the refined selenium obtained by the method realizes the step-by-step efficient removal of impurities of copper, lead and tellurium in the crude selenium powder; the yield of the refined selenium is more than 99 percent, and the loss of the selenium is small; the purity of the selenium in the refined selenium can reach 99.99 percent, and the purity of the selenium is high; copper, lead and tellurium are deeply removed, and the removal rate is more than 99.9%; and the method has simple process and is easy to operate and master.
Drawings
FIG. 1 is a process flow chart of the method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential according to the invention.
Detailed Description
The invention provides a method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential, which comprises the following steps:
mixing the copper smelting crude selenium powder to obtain selenium slurry;
after the selenium slurry is subjected to first pH value adjustment, adding an oxidant to an oxidation potential, sequentially performing a first precipitation reaction and a first filtration to remove copper and lead in copper smelting crude selenium powder to obtain primary selenium; the oxidation potential is 400-800 mV;
mixing the primary selenium and a reducing agent to a reduction potential, carrying out second pH value adjustment, and then sequentially carrying out second precipitation reaction and second filtration to remove tellurium in copper smelting crude selenium powder; the reduction potential is-400-0 mV.
In the present invention, the components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention carries out size mixing on copper smelting crude selenium powder to obtain selenium slurry.
In the invention, the chemical components of the copper smelting crude selenium powder preferably comprise, by mass percent: 60-80% of Se, 1-10% of Te, 0.01-5% of Cu, 0.01-5% of Pb and H25-30% of O, and the balance of trace impurity elements Fe, S, Sn, As and Ni. In the invention, the particle size of the copper smelting crude selenium powder is preferably 0.1-300 μm, more preferably 50-275 μm, and still more preferably 100-250 μm. In the invention, the copper smelting crude selenium powder is preferably derived from copper smelting crude selenium powder produced in the comprehensive recovery process of crude copper electrolytic refining anode mud.
The present invention is not particularly limited to the slurry mixing, and the slurry mixing may be performed by using a method known to those skilled in the art, specifically, stirring. In the invention, the mass ratio of copper smelting crude selenium powder to water in the selenium slurry is preferably 1: (1-2), more preferably 1: (1.2-1.8), and more preferably 1: (1.4-1.6).
After the selenium slurry is obtained, the selenium slurry is subjected to first pH value adjustment, then an oxidant is added to the selenium slurry to reach an oxidation potential, and a first precipitation reaction and a first filtration are sequentially performed to remove copper and lead in copper smelting crude selenium powder, so that primary selenium is obtained.
In the present invention, after the first pH adjustment, the pH of the obtained slurry is preferably 1 to 4, more preferably 1.5 to 3.5, and still more preferably 2 to 3. In the present invention, the first pH adjuster is preferably a non-oxidizing acid, and is preferably dilute sulfuric acid. In the present invention, the mass concentration of the dilute sulfuric acid is preferably 10 to 60%, more preferably 20 to 50%, and still more preferably 30 to 40%.
In the present invention, the oxidizing agent is preferably one or more of potassium permanganate, sodium hypochlorite, hydrogen peroxide and manganese dioxide. In the present invention, the oxidizing agent is preferably provided in the form of an oxidizing agent solution; the mass concentration of the oxidant solution is preferably 0.5-30%, more preferably 2-28%, and still more preferably 5-25%. In the present invention, the oxidation potential is 400 to 800mV, preferably 450 to 750mV, and more preferably 500 to 700 mV.
In the present invention, the oxidizing agent is preferably added under stirring; the stirring rate is not particularly limited in the present invention, and a stirring rate known to those skilled in the art may be used. In the invention, the addition rate of the oxidant is preferably 5-30 mL/min/1kg of copper smelting crude selenium powder, more preferably 8-27 mL/min/1kg of copper smelting crude selenium powder, and further preferably 10-20 mL/min/1kg of copper smelting crude selenium powder. The present invention prevents exothermic expansion due to too fast oxidant addition by controlling the oxidant addition rate.
In the present invention, electrons at the oxidation potential are accepted by the oxidant, and the chemical reaction formula is:
PbSe(s)-2e=Se(s)+Pb2+(aq);
CuSe(s)-2e=Se(s)+Cu2+(aq)。
in the present invention, the first precipitation is preferably carried out under stirring; the stirring speed is preferably 30-300 rpm, more preferably 50-270 rpm, and further preferably 80-220 rpm; the time is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and still more preferably 1.5 to 2 hours.
The first filtration is not particularly limited in the present invention, and filtration known to those skilled in the art, specifically, suction filtration, may be employed. The invention realizes solid-liquid separation by filtration, the obtained filtrate contains lead and copper ions, and the obtained filtrate can be recycled for refining lead and copper; the obtained filter cake is the primary selenium with improved copper, lead and selenium content.
After the first filtration, the present invention preferably further comprises a post-treatment; the post-treatment preferably comprises washing and filtration. The method further removes the lead ions and the copper ions adhered to the primary selenium by washing, thereby improving the removal rate of the lead and the copper; the filtration is not particularly limited in the present invention, and filtration known to those skilled in the art may be employed.
After the primary selenium is obtained, the primary selenium and a reducing agent are mixed to a reduction potential, and after a second pH value is adjusted, a second precipitation reaction and a second filtration are sequentially carried out to remove tellurium in the copper smelting crude selenium powder.
In the present invention, the reducing agent is preferably a ferrous salt or a sulfite. In the present invention, the reducing agent is preferably provided in the form of a reducing agent solution; the mass concentration of the reducing agent solution is preferably 0.5-30%, more preferably 2-28%, and still more preferably 5-25%. In the present invention, after the second pH adjustment, the pH of the obtained slurry is preferably 7 to 12, more preferably 7.5 to 11.5, and still more preferably 8 to 11. In the present invention, the second pH adjuster is preferably an alkali which does not react with the first pH adjuster to produce a hardly soluble product, and more preferably sodium carbonate or sodium hydroxide. In the present invention, the sodium carbonate is preferably a saturated sodium carbonate solution. In the present invention, the reduction potential is-400 to 0mV, preferably-350 to-50 mV, and more preferably-300 to-100 mV.
In the present invention, the electrons at the reduction potential are provided by a reducing agent, and the chemical reaction formula is as follows:
Te+3H2O-4e=TeO3 2-+6H+
in the present invention, the second precipitation is preferably carried out under stirring; the stirring speed is preferably 30-1000 rpm, more preferably 50-900 rpm, and further preferably 100-800 rpm; the time is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and still more preferably 1.5 to 2 hours.
The second filtration is not particularly limited in the present invention, and filtration known to those skilled in the art may be used, specifically, suction filtration. The solid-liquid separation is realized through filtration, the obtained filtrate contains tellurium ions, and the obtained filtrate can be recycled for tellurium extraction; the obtained filter cake is refined selenium with tellurium removed and selenium content further improved.
After the second filtration, the present invention preferably further comprises a post-treatment; the post-treatment preferably comprises washing, filtration and drying. The method further removes the tellurium ions adhered to the primary selenium by washing, thereby improving the removal rate of the tellurium; the filtration is not particularly limited in the present invention, and filtration known to those skilled in the art may be employed. In the invention, the drying temperature is preferably 80-110 ℃, and more preferably 85-105 ℃; the time is preferably 1 to 10 hours, and more preferably 2 to 9 hours. In the present invention, the drying is preferably vacuum drying, forced air drying or microwave drying.
FIG. 1 is a process flow chart of the method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential according to the invention.
In order to further illustrate the present invention, the method for removing copper, lead and tellurium from copper smelting crude selenium powder by controlling potential provided by the present invention is described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The copper smelting crude selenium powder comprises the following components in percentage by mass: se 75.04%, Te 7.08%, Pb 2.78%, Cu 4.7%, and the balance of water, Fe and other impurities;
adding 1L of deionized water into 1kg of copper smelting crude selenium powder, stirring and mixing to obtain selenium slurry;
adding 390mL of dilute sulfuric acid with the mass concentration of 25% into the obtained selenium slurry, adjusting the pH value of a selenium slurry system to be 1, adding 51mL of oxidant potassium permanganate solution with the mass concentration of 10% into the selenium slurry at the adding rate of 20mL/min/1kg of copper smelting crude selenium powder, stirring at 500rpm, controlling the oxidation potential of the system to be 600mV, converting impurities Cu and Pb into soluble ions, stirring for 1.5h, performing filter pressing on the material, washing to be neutral, and removing Cu and Pb to obtain primary selenium;
adding 43mL of reducing agent ferrous sulfate solution with the mass concentration of 10% into the primary selenium, regulating and controlling the potential of the system to be kept at-100 mV, adding 510mL of saturated sodium carbonate solution to regulate the pH value of the system to be 10, stirring at the stirring speed of 500rpm for 1.5h to convert impurity tellurium into soluble tellurite radical ions, washing and filtering to obtain filter residue with impurity tellurium removed, and vacuum-drying the obtained filter residue at 80 ℃ for 6h to obtain the refined selenium.
The weight of the obtained refined selenium in this example was 744 g.
Calculating the yield of the refined selenium according to the formula I:
the refined selenium yield of example 1 is calculated to be 99.1%.
Detecting the fine selenium by adopting an inductively coupled plasma mass spectrometer (ICP-MS) according to non-ferrous metal industry standards YS/T223-2007 and YS/T226.13-2009 of the people's republic of China; the detection result is as follows: by mass percentage, Se 99.991%, Cu 0.0002%, Pb 0.0003% and Te 0.0006%.
Example 2
The copper smelting crude selenium powder comprises the following components in percentage by mass: 63.9 percent of Se, 9.31 percent of Te, 2.78 percent of Pb, 1.7 percent of Cu, and the balance of water, Fe and other impurities;
adding 0.5L of deionized water into 1kg of copper smelting crude selenium powder, and stirring and mixing to obtain selenium slurry;
adding 260mL of dilute sulfuric acid with the mass concentration of 30% into the obtained selenium slurry, adjusting the pH value of a selenium slurry system to be 2, adding 60mL of oxidant sodium hypochlorite solution with the mass concentration of 15% into the selenium slurry at the adding rate of 30mL/min/1kg of copper smelting crude selenium powder, stirring at 500rpm, controlling the oxidation potential of the system to be 500mV, converting impurities Cu and Pb into soluble ions, stirring for 2 hours, performing filter pressing on the material, and washing to be neutral, thereby removing Cu and Pb and obtaining primary selenium;
adding 39mL of reducing agent ferrous chloride with the mass concentration of 15% into the primary selenium, regulating and controlling the potential of the system to be kept at-50 mV, adding 360mL of saturated sodium carbonate solution to regulate the pH of the system to be 9, stirring at the stirring speed of 500rpm for 2h to convert impurity Te into soluble ions, washing and filtering to obtain filter residue with impurity Te removed, and drying the obtained filter residue by air blowing at 100 ℃ for 4h to obtain the refined selenium.
The weight of the refined selenium obtained in this example was 635.8 g.
The refined selenium yield of example 2 was 99.5% calculated according to formula I.
The content of the obtained refined selenium was determined according to the test standards and test methods of example 1. The test results are: by mass percentage, Se is 99.993%, Cu is 0.0001%, Pb is 0.0002%, and Te is 0.0004%.
Example 3
The copper smelting crude selenium powder comprises the following components in percentage by mass: 78.9 percent of Se, 8.31 percent of Te, 1.78 percent of Pb, 4.7 percent of Cu4, and the balance of water, Fe and other impurities;
adding 0.8L of deionized water into 1kg of copper smelting crude selenium powder, and stirring and mixing to obtain selenium slurry;
adding 305mL of dilute sulfuric acid with the mass concentration of 28% into the obtained selenium slurry, adjusting the pH of the system to be 1.5, adding 41mL of oxidant hydrogen peroxide solution with the mass concentration of 30% into the selenium slurry at the adding rate of 50mL/min/1kg of copper smelting crude selenium powder, stirring at 800rpm, controlling the oxidation potential of the system to be 450mV, converting impurities Cu and Pb into soluble ions, stirring for 1h, performing filter pressing on the material, and washing to be neutral, thereby removing Cu and Pb and obtaining primary selenium;
adding 68mL of reducing agent ferrous sulfate solution with the mass concentration of 20% into the primary selenium, regulating and controlling the potential of the system to be kept at-300 mV, adding 393mL of saturated sodium carbonate solution to regulate the pH of the system to be 9.5, stirring at the stirring speed of 800rpm for 0.5h to convert impurity tellurium into soluble ions, washing and filtering to obtain filter residue with impurity tellurium removed, and carrying out forced air drying on the obtained filter residue at the temperature of 110 ℃ for 3h to obtain the refined selenium.
The weight of the refined selenium obtained in this example was 784 g.
The refined selenium yield of example 1 is calculated to be 99.4%.
The content of the obtained refined selenium was determined according to the test standards and test methods of example 1. The test results are: by mass percentage, Se is 99.993%, Cu is 0.0005%, Pb is 0.0001%, and Te is 0.0001%. The embodiment shows that the method for removing copper, lead and tellurium in the copper smelting crude selenium powder by controlling the potential realizes the efficient removal of impurities of copper, lead and tellurium in the copper smelting crude selenium powder, has the characteristics of high selenium yield, small selenium loss and simple process, and the selenium product prepared by the method has high purity, can meet the use requirement of advanced materials, and has good economic value and industrial application value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A method for removing copper, lead and tellurium in copper smelting crude selenium powder by controlling potential is characterized by comprising the following steps:
mixing the copper smelting crude selenium powder to obtain selenium slurry;
after the selenium slurry is subjected to first pH value adjustment, adding an oxidant to an oxidation potential, sequentially performing a first precipitation reaction and a first filtration to remove copper and lead in copper smelting crude selenium powder to obtain primary selenium; the oxidation potential is 400-800 mV; after the first pH value is adjusted, the pH value of the obtained slurry is 1-4;
mixing the primary selenium and a reducing agent to a reduction potential, carrying out second pH value adjustment, and then sequentially carrying out second precipitation reaction and second filtration to remove tellurium in copper smelting crude selenium powder; the reduction potential is-400-0 mV; and after the second pH value is adjusted, the pH value of the obtained slurry is 7-12.
2. The method according to claim 1, wherein the chemical composition of the copper smelting crude selenium powder comprises the following components in percentage by mass: 60-80% of Se, 1-10% of Te, 0.01-5% of Cu, 0.01-5% of Pb and H25-30% of O, and the balance of trace impurity elements Fe, S, Sn, As and Ni.
3. The method according to claim 1 or 2, wherein the particle size of the copper smelting crude selenium powder is 0.1-300 μm.
4. The method of claim 1, wherein the oxidizing agent is one or more of potassium permanganate, sodium hypochlorite, hydrogen peroxide, and manganese dioxide.
5. The process according to claim 1, characterized in that the first precipitation reaction is carried out under stirring conditions; the stirring speed is 30-300 rpm, and the time is 0.5-3 h.
6. The method of claim 1, wherein the reducing agent is a ferrous salt or a sulfite salt.
7. The process according to claim 1, characterized in that the second precipitation reaction is carried out under stirring conditions; the stirring speed is 30-1000 rpm, and the time is 0.5-3 h.
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